Process for producing certain 2-aminophenoldisulfonamides



PROCESS FOR PRODUCING CERTAIN Z-AMINO- PHENOLDISULFONAMIDES William H. Armento, Albany, and William E. Wallace, Rensselaer, N.Y., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Dec. 23, 1957, Ser. No. 704,241

6 Claims. c1. zen-241.1

This invention relates to novel compounds and to novel methods for producing same. More particularly, the compounds of the instant invention are Z-aminophenoldisulfonamides having the formula:

wherein R and R are'selected from the group consisting of H, alkyl, aralkyl, cycloalkyl, and aryl, and when taken together, the atoms necessary to form a heterocycle. The compounds of the instant invention have been found to be highly effective as diazo components in the production of metallizible azo dyestuffs, asdisclosed and claimed in our copending application Serial No. 104,312, filed on even date herewith.

In the above formula, R and R may be the same or different, and may be H, alkyl such as octadecyl, decyl, and preferably lower alkyl such as methyl, ethyl, propyl, isobutyl and hexyl, cycloalkyl such as cyclohexyl, aralkyl such as benzyl, aryl such as phenyl and biphenyl, and when taken together, morpholinyl, piperidinyl, pyridyl, and the like. It will be understood that 'R and R as above defined may contain inert substituents such as hydroxy, lower alkoxy such as methoxy, ethoxy, and the like.

The process of the instant invention for producing the above defined compounds comprises heating one mole of benzoxazolone with a minimum of about 4 up to about 12 moles of chlorosulfonic acid at a temperature of about 90 to 120 C. for about 3 to hours, treating the resulting benzoxazolone disulfonylchloride with at least 4 moles of a compound of the formula R R NH, wherein R 'and R have the values given above, and then subjecting the resulting benzoxazolone disulfonamide to aqueous alkaline hydrolysis conditions.

In carrying out the first step of the instant process, the benzoxazolone and chlorosulfonic acid are preferably admixed at a low temperature, i.e. less than about 10 C., and the temperature slowly raised and maintained at a temperature of 90 to 120 C. for sufficient time to complete the reaction, usually from about 3 to 10 hours. Temperatures above 10 C. and up to 120 C. may be employed for the initial admixture step, but are not preferred since thechlorosulfonic acid is more difficult to work at higher temperatures. Since this initial reaction probably proceeds in two stages, in the first of which the benzoxazolone disulfonic acid is first formed, and in the second of which the disulfonic acid reacts with two more moles of chlorosulfonic acid, 4 moles of chlorosulfonic acid are theoretically required to form the benzoxazolone disulfonylchloride, having the formula o----co NH (SOzCD However, an amount in excess of this theoretical amount,

- .up to about- 12'moles of the chlorosulfonic acid per mole of the benzoxazolone is preferred to prevent formation of undesirable by-products.

Reaction of the disulfonyl chloride with ammonia or an amine toproduce the corresponding disulfonamide is readily carried out at ordinary temperatures by mere admixture. Here again, 4 moles of the amidating compound of the formula R R NH are theoretically required for each mole of the disulfonylchloride, although it is preferred to employ an excess of up to about 14 moles for neutralization of acidic substances and thelike. As representative of suitable compounds for this amidation there may be mentioned ammonium hydroxide, ammonium carbonate; methylamine, ethylamine,methylethyl amine,'diethylamine, dimethylatnine, propylamine, isobutylamine, ethanolamine, diethanolamine, "propanol amine, hexylamine, decylamine, octadecylamine, methylethanolamine, benzylamine, methylbenzylamine, cyclohexylamine, aniline, toluidine, xylidine, anisidine, morpholine, piperidine, pyridine, and the lke.

'In general, this amidating step may be carried out be tween the disulfonylchloride and the amidating compound alone or in aqueous or organic solvent solution or dispersion at temperatures ranging from about 5 to 30 C. for periods ranging from about 1 to 24 hours. Concentrated solutions of the ammonia or amine compound are preferred, but such concentrations may range from about 30 to 100% by weight of said compound. As compatible solvents which are inert under thev conditions of amidation, there may be mentioned chlorobenzene, trichlorobenzene, nitrobenzene, toluene, dioxane, carbon tetrachloride, ether and the like. Upon completion of the amidating reaction, the disulfonamide is filtered and sucked dry. It has the formula sis conditions to produce the desired 2-arninophenoldiually employing about a 15 to- 35% by volume caustic soda solution using a minimum of two equivalents of caustic up to about 300% of theory. Other alkaline substances may be employed, as for example, potassium hydroxide and the like. elevated temperatures, usually at or near the boil, for sufficient time to open the benzoxazolone ring, usually from about 1 to 10 hours. The hydrolysis medium is then neutralized with acid, for example by acidification to Congo acid followed by cooling, filtering and washing. The following examples, in which parts are by weight unless otherwise indicated are illustrative of the instant invention and are not to be regarded as limitative.

Example 1 Charge to a 500 cc. 3-neck flask fitted with an agitator and thermometer, 350 g. chlorosulfonic acid. Cool to 5 C. Add 50 g. 100% benzoxazolone dry at such a rate that the temperature does not exceed 10 C.

Allow to warm during 1 hour to room temperature.

Heat to l00-110 C. during 1 hour and hold at that temperature for 4 to 5 hours. Cool to room temperature and pour onto crushed ice. Filter and wash with ice water until almost neutral to Congo paper. Add the paste to an aqueous solution of ethylamine containing g. of ethylamine which is kept below 10 C. during Patented Apr. 11, 1961 The hydrolysis is carried out at- I aemroa In the above example, the ethylamine may be replaced by'ammoniurn hydroxide, methyl amine, dimethylamine, ethylamine, diethylamine, propylamine, isob-utylamine, ethanolamine, diethanolamine, propanolamine, methylethanolamine, benzylamine, methylhenzylamine, cyclohexylamine, ammonium carbonate, morpholine, piperi-. dine, pyridine and, the like, as exemplified by the followingexamples,

Example 2 7 Example 1 is repeated but substituting for the ethyl: amine, the same amount of dimethylamine. Theproduct has the structure Example 3 Example 1 is repeated but substituting for the ethylamine, 95 g. ethanolamine. The product has the structure Example 4 Example 1 is repeated but substituting for the ethylamine, 153 g. 'cyclohexylamine. The product has the formula [HUCAHNO :Sh:

Example 5 Example 1, isrepeated but substitutingfor the ethylamine, 135 g. morpholine. The product has theformula Ex mpl fil Example 1 is repeated but substituting for the ethylamine, 102 cc. NH OH 29' Be; The product-hasthe formula Example 7 Example 1 is repeated but substituting for the; ethylamine, 140 g. aniline. The product has the formula lg lfs I Example 8 Example 1 is repeated; but substituting for the ethylamine, 160 g. benzylamine. The product has the formula NH; [O-cmrmms] Example 9 Example 1 is repeated but substituting forthe ethylamine, 128 g. piperidine. The product has the formula This invention has been disclosed with respect to cer tain preferred embodiments, and there will become obvious to persons skilled in the art various modifications; equivalents or variations thereof which are intended to be included within the spirit and scope of this invention.

We claim:

1, A process for producing a compound having the formula wherein R and'IR are selected from the group consisting of H, alkyl, aralkyl, cycloalkyl, and aryl, and when taken together, the atoms necessary to form a heterocycle, comprising heating one mole of benzoxazolone with at least about 4 up to about 12 moles of chlorosulfonic acid at a temperature of about to C. for about 3 to 10 hours, treating the resulting benzoxazolone disulfonylchloride with at least 4 moles of an amine compound of the formula R R NH wherein R, and R are selected from the group consisting of H, alkyl, aralkyl, cycloalkyl, and aryl, and when taken together, the atoms necessary to complete a heterocycle, and then subjecting the resulting benzoxazolone disulfonamide to aqueous alkaline hydrolysis conditions.

2. A process as defined in claim 1 wherein said amine compound is ethylamine.

3. A process as defined in claim 1 wherein said amine compound is dimethylamine.

4. A process as defined in claim 1 wherein said amine compound is cyclohexylamine.

5. A process as defined in claim 1 wherein said amine compound is morpholine.

6. A process as defined in claiml wherein said amine compound is ammonia.

References Cited in the file of this patent UNITED STATES PATENTS Schetty et a1. Dec. 24, 1957 Strobei et a1. May 13, 1958 OTHER REFERENCES 5 Scudi et al.: J. Amer. Chem. Soc., vol. 63, page 879 Elderfield: .Heterocyclic Compounds, vol. 5, pages Migrdichian: Organic Synthesis, vol. 2, pages 1688, 10 1690-1 (1957). 

1. A PROCESS FOR PRODUCING A COMPOUND HAVING THE FORMULA 